JP2012523487A - Adhesives from polymers with crystalline domains, amorphous polyurethanes and silane compounds - Google Patents

Abstract

  An adhesive from two components is described, wherein the first component contains at least two different polymers, at least one of which has a carboxyl group. At least one of the polymers is selected from a polymer capable of forming a crystalline domain and a copolymer from ethylene and vinyl acetate, and the second polymer is an amorphous polyurethane, wherein the first The weight ratio of polymer to second polymer is 2: 8 to 8: 2. The second component contains at least one silane compound reactive to a carboxyl group. Adhesives can be used to produce film laminated molded parts for automobile manufacturing that have high climate change stability.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an adhesive from two components, wherein the first component contains at least two different polymers, of which at least one of the polymers has a carboxyl group, and Wherein the first polymer is selected from polymers capable of forming crystalline domains, copolymers from ethylene and vinyl acetate and mixtures thereof, and the second polymer is an amorphous polyurethane, and Here, the second component contains at least one silane compound reactive to the carboxyl group. Adhesives can be used to produce film laminated molded parts for automobile manufacturing that have high climate change stability. The invention also relates to a method for producing a film-laminated molded part for automobile production using the adhesive according to the invention.

  For the production of composites for mounting on vehicles, for example for the production of automotive interior parts, a suitable plastic film is permanently applied with adhesive to a shaped body, for example from plastic, metal or fiber metal. Given. For this purpose, polyurethane-based aqueous dispersion adhesives can be used. To improve applied technical properties, isocyanates have frequently been used as crosslinkers. What is desired is an isocyanate-free system. From WO2008 / 006733 an aqueous polyurethane adhesive having a silane compound as additive is known. The known adhesive dispersions are still not optimal in all respects, especially with regard to climate and temperature loading behavior.

  Shaped composites used in automobiles are frequently exposed to changing climate and temperature loads. At that time, in particular, in the range of bending or bending of the molded member, the adhesion may be quickly lost with time, and the laminated polymer film may peel from the molded member in some places. Therefore, what is desired is an adhesive with high climate change stability.

  The object of the present invention was to further improve the applied technical properties of polyurethane dispersions for industrial lamination, in particular with regard to the good climate and temperature load behavior of mounting members in vehicles.

The subject of the present invention is an adhesive from the first aqueous component and from the second component,
Here, the first component contains at least one first polymer and at least one second polymer different from the first polymer,
Wherein the first polymer is selected from polymers capable of forming crystalline domains (hereinafter also referred to as crystalline polymers), copolymers from ethylene and vinyl acetate, and mixtures of these polymers;
And the second polymer is an amorphous polyurethane, and
Here, at least one of both polymers has a carboxyl group,
Where the mass ratio of the first polymer to the second polymer is from 2: 8 to 8: 2, and
Here, the second component contains at least one silane compound reactive to the carboxyl group. The first polymer is in particular a polymer that enhances the climate change stability of a film-laminated molded part made with an adhesive as compared to a second polymer used alone.

  The two components are preferably held separately before use on a substrate and are mixed with each other only before use.

  The subject of the invention is also the use of an adhesive according to the invention for the production of film-laminated molded parts for automobile production having a high climate change stability, or for the climate of film-laminated molding parts for automobile production. It is used to increase fluctuation stability.

  A high climate change stability is achieved after more than one test cycle of the climate change test, preferably after more than 5 or more than 10 test cycles, particularly advantageously after more than 20 test cycles (one cycle). 4 h storage at 90 ° C. and 80% humidity, 2 h cooling to −30 ° C., 4 h storage at −30 ° C. and 10% relative humidity and 2 h heating to 90 ° C.), eg, BMW test According to PR 308.2 (2006-04) “Klimatische Pruefung von Kleberbindgen”, it means that no clear peeling of the soft PVC film adhered to the specimen has occurred.

  A polymer capable of forming a crystalline domain is a polymer having a crystalline domain when present as a polymer film in a pure form at room temperature (20 ° C.). The polymer film then consists entirely or partly of crystalline domains, i.e. it is not completely amorphous. The presence of the crystal domain can be confirmed by DSC measurement, for example, measurement of crystallite melting enthalpy.

  Preferably, the first polymer is a polymer having a heat of fusion of at least 20 J / g when present as a polymer film. Preferably, the first polymer is crystalline in the pure state and has a melting point in the range of 30-150 ° C.

In one embodiment, the first polymer is
Selected from the group consisting of (i) a polyurethane forming a crystalline domain having units derived from a polyester diol; and (ii) an ethylene / vinyl acetate copolymer;
Here, the second polymer is preferably an amorphous polyurethane having units derived from polyether diol.

  In one embodiment, the first polymer is a crystalline polyurethane and has units derived from a polyester diol, and the second polymer is an amorphous polyurethane and is derived from a polyether diol. Where at least one of both polyurethanes has a carboxyl group and is the sum of all units derived from the polyester diol versus the sum of all units derived from the polyether diol. The mass ratio is preferably 2: 9 to 7: 2.

Preferably, the first component of the adhesive is
(A) (i) polyurethanes having crystalline domains and having units derived from polyester diols and no units derived from polyether diols and (ii) ethylene / vinyl acetate copolymers or their 20-80 parts by weight, preferably 40-70 parts by weight of at least one first polymer selected from the mixture,
(B) 20-80 parts by weight of at least one amorphous polyurethane having units derived from polyether diol and not having units derived from polyester diol; and (c) (a) and Still another polymer different from (b), for example polyvinyl acetate, polyacrylate copolymer dispersion or styrene / butadiene dispersion 0-50 parts by weight, preferably 10-40 parts by weight.

Preferably, the first polymer is polyurethane and a) a diisocyanate,
b) a polyester diol having a molecular weight of greater than 500 to 5000 g / mol,
c) a diol having a carboxylic acid group, and d) optionally a reactive group selected from an alcoholic hydroxy group, a primary amino group, a secondary amino group and an isocyanate group different from a) to c). It is synthesized from still another monovalent compound or polyvalent compound.

  Preference is given to polyurethanes in which the polyester units account for 80 to 90% by weight of the polymer.

Preferably, the second polymer is polyurethane and a) a diisocyanate,
b) a polyether diol having a molecular weight of 240 to 5000 g / mol,
c) a diol having a carboxylic acid group, and d) optionally a reactive group selected from an alcoholic hydroxy group, a primary amino group, a secondary amino group and an isocyanate group different from a) to c). It is synthesized from still another monovalent compound or polyvalent compound.

  Preference is given to polyurethanes in which the polyether units comprise 70 to 80% by weight of the polymer.

  Preferably, the second polymer polyether diol is selected from polytetrahydrofuran and polypropylene oxide. Preferably, the polyester diol of the first polymer is selected from the reaction product of a dihydric alcohol and a divalent carboxylic acid and a lactone based polyester diol.

  Preferably, the polyurethanes are each synthesized from at least 40% by weight, particularly preferably at least 60% by weight and very particularly preferably at least 80% by weight from diisocyanates, polyether diols or polyester diols. The first polyurethane preferably has a polyester diol in an amount of more than 10% by weight, particularly preferably more than 30% by weight, in particular more than 40% by weight, based on the first polyurethane. In an amount or greater than 50% by weight, very advantageously greater than 60% by weight. The second polyurethane preferably has a polyether diol in an amount of more than 10% by weight, particularly preferably more than 30% by weight, in particular more than 40% by weight, based on the second polyurethane. It is contained in a large amount or in an amount greater than 50% by weight, very advantageously in an amount greater than 60% by weight.

  In one embodiment, the first component contains at least 40% by weight of polyurethane (amorphous polyurethane or a mixture of amorphous and crystalline polyurethane), based on solids. In yet another embodiment, the first component contains 10-75 parts by weight ethylene / vinyl acetate copolymer as the first polymer, based on solids.

  Preferably, at least the first polyurethane is crystalline in the pure state. The first polyurethane preferably has a melting point greater than 30 ° C., in particular greater than 40 ° C., particularly advantageously greater than 50 ° C., or rather greater than 60 ° C. or greater than 70 ° C .; The melting point is not greater than 150 ° C., in particular not greater than 100 ° C. The melting point is therefore in particular in the range from 30 to 150 ° C., particularly preferably in the range from 40 to 150 ° C. and very particularly preferably in the range from 50 to 100 ° C. and in particular from 50 to 80 ° C. Is in range. The second polyurethane is amorphous in the pure state. The first polyurethane preferably has a melting enthalpy greater than 20 J / g. The melting point and melting enthalpy are measured by the differential scanning calorimetry method. The measurement is performed using a polyurethane film having a thickness of 200 μm that is dried at 40 ° C. for 72 hours in a forced air circulation furnace before the measurement. In order to prepare for the measurement, about 13 mg of polyurethane is filled in the pan. The pan is closed, the sample is heated to 120 ° C., cooled at 20 K / min, and conditioned at 20 ° C. for 20 hours. The sample thus prepared is measured by the DSC method according to DIN 53765, where the sample is heated at 20 K / min. As the melting temperature, the peak temperature according to DIN 53765 is used, and the melting enthalpy is calculated as shown in FIG. 4 of DIN 53765.

  Suitable diisocyanates are, for example, those of the formula X (NCO) 2, where X is an aliphatic hydrocarbon group having 4 to 15 C atoms, an alicyclic carbonization having 6 to 15 C atoms. It represents a hydrogen group, an aromatic hydrocarbon group or an araliphatic hydrocarbon group having 7 to 15 C atoms. Examples of such diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI) 2,2-bis- (4-isocyanatocyclohexyl) -propane, trimethylhexane diisocyanate, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4, 4'-diisocyanato-diphenylmethane, 2,4'-diisocyanato-diphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), bis- (4-isocyanato-cyclohexyl) Isomer Tan (HMDI), for example, trans / trans isomers, the cis / cis isomer and cis / trans isomers as well as mixtures consisting of these compounds. Such diisocyanates are commercially available.

  Of particular importance as mixtures of these isocyanates are mixtures of the respective structural isomers of diisocyanatotoluene and diisocyanato-diphenylmethane, in particular 80 mol% of 2,4-diisocyanatotoluene and 2,6-di- A mixture from 20 mol% isocyanatotoluene is suitable. Furthermore, mixtures of aromatic isocyanates such as 2,4-diisocyanatotoluene and / or 2,6-diisocyanatotoluene and aliphatic or alicyclic isocyanates such as hexamethylene diisocyanate or IPDI are particularly preferred, The preferred mixing ratio of aliphatic isocyanate to aromatic isocyanate is from 1: 9 to 9: 1, in particular from 1: 4 to 4: 1.

  For the synthesis of polyurethanes, in addition to the compounds mentioned above, it is also possible to use, in addition to free isocyanate groups, further isocyanates with capped isocyanate groups, for example uretdione groups.

  In view of good film formation and elasticity, relatively high molecular weight diols having a molecular weight of mainly greater than 500 and up to 5000 g / mol, preferably about 1000 to 3000 g / mol, are taken into account as polyester diols and polyether diols. It is done. This is the number average molecular weight Mn. Mn is determined by determining the number of end groups (OH number).

Polyester diols are known, for example, from pages 62 to 65 of Ullmanns Enzyklopaedie der technischen Chemie, 4th edition, volume 19. Preference is given to using polyester diols obtained by reaction of dihydric alcohols with divalent carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides or the corresponding polycarboxylic esters of lower alcohols or mixtures thereof can also be used for the production of polyester polyols. The polycarboxylic acid may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic and may optionally be substituted, for example by halogen atoms and / or unsaturated. . Examples of this include: suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endo Methylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid. Preference is given to dicarboxylic acids of the general formula HOOC— (CH ₂ ) _y —COOH, wherein y is a number from 1 to 20, preferably an even number from 2 to 20, such as succinic acid, adipic acid, Sebacic acid and dodecanedicarboxylic acid.

Examples of the dihydric alcohol include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, Pentane-1,5-diol, neopentyl glycol, bis- (hydroxymethyl) -cyclohexane, such as 1,4-bis- (hydroxymethyl) cyclohexane, 2-methyl-propane-1,3-diol, methylpentanediol, In addition, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol are taken into account. Preference is given to alcohols of the general formula HO— (CH ₂ ) _x —OH, wherein x is a number from 1 to 20, preferably an even number from 2 to 20. Examples in this regard are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Further advantageous is neopentyl glycol.

  In addition to the polyester diol or polyether diol, in some cases, for example, a polycarbonate diol such as can be obtained by reaction of phosgene with an excess of low molecular weight alcohols listed as synthesis components for polyester polyols. You can do it.

Optionally, lactone-based polyester diols may also be used, which may contain terminal hydroxyl groups with lactones added to homopolymers or mixed polymers of lactones, preferably to suitable bifunctional initiator molecules. Product. As lactones, advantageously the general formula HO— (CH ₂ ) _z —COOH [z is a number from 1 to 20 and the H atom of the methylene unit is also substituted by a C _{1 to} C ₄ -alkyl group. Derived from the compound of [may be]. Examples are e-caprolactone, β-propiolactone, g-butyrolactone and / or methyl-e-caprolactone and mixtures thereof. Suitable initiator components are, for example, the low molecular weight dihydric alcohols mentioned above as synthesis components for polyester polyols. The corresponding polymer of ε-caprolactone is particularly advantageous. Lower polyester diols or polyether diols may also be used as initiators for producing lactone polymers. Instead of polymers of lactones, the corresponding chemically equivalent polycondensates of hydroxycarboxylic acids corresponding to lactones may also be used.

Polyether diols are in particular produced by polymerization with ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin itself, for example in the presence of BF ₃ , or optionally mixed with these compounds. Or, in turn, starting components having reactive hydrogen atoms, such as alcohols or amines such as water, ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-bis (4- It can be obtained by addition to hydroxyphenyl) -propane or aniline. Particular preference is given to polypropylene oxide, polytetrahydrofuran with a molecular weight of 240 to 5000 and in particular 500 to 4500. Preference is given to polyether diols comprising less than 20% by weight of ethylene oxide.

  Optionally, a polyhydroxyolefin, preferably one having two terminal hydroxyl groups, for example α, ω-dihydroxypolybutadiene, α, ω-dihydroxypolymethacrylate or α, ω-dihydroxypolyacrylic ester, can also be used as monomer (c1). ) Can be used together. Such compounds are known, for example, from EP-A 622378. Still other suitable polyols are polyacetals, polysiloxanes and alkyd resins.

The hardness and elastic modulus of the polyurethane, if necessary, is different from those in addition to the polyester diol, in addition to the polyester diol, or about 60-500, preferably 62-200 g / mol. This can be increased when a low molecular weight monomer diol having a molecular weight is used. As low molecular weight monomer diols, the synthesis components for short-chain alkanediols mentioned for the production of polyester polyols are used, in particular, where non-carbon having 2 to 12 C atoms and an even number of C atoms. Preference is given to branched diols and pentane-1,5-diols and neopentyl glycols. Examples are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,3-diol, butene-1,4-diol, butyne-1,4-diol, pentane-1, 5-diol, neopentyl glycol, bis- (hydroxymethyl) -cyclohexane, such as 1,4-bis- (hydroxymethyl) cyclohexane, 2-methyl-propane-1,3-diol, methylpentanediol, as well as diethylene glycol, Triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol are taken into account. Preference is given to alcohols of the general formula HO— (CH ₂ ) _x —OH, wherein x is a number from 1 to 20, preferably an even number from 2 to 20. Examples in this regard are ethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol and dodecane-1,12-diol. Further advantageous is neopentyl glycol.

  Advantageously, the proportion of polyester diol or polyether diol is 10 to 100 mol%, based on the total amount of all diols, and the proportion of low molecular weight monomer diol is based on the total amount of all diols. 0 to 90 mol%. The ratio of polymer diol to monomer diol is particularly preferably from 0.1: 1 to 5: 1, particularly preferably from 0.2: 1 to 2: 1.

  In order to achieve the water dispersibility of the polyurethane, the polyurethane is converted into at least one isocyanate group or at least one group reactive to isocyanate groups, and also at least one hydrophilic group or hydrophilic group. A monomer having at least one group which may be obtained may additionally be included as a synthesis component. In the text below, the term “hydrophilic group or potential hydrophilic group” is abbreviated as “(potential) hydrophilic group”. The (latent) hydrophilic group reacts with the isocyanate much more slowly than the functional groups of the monomers utilized in the synthesis of the polymer backbone. The proportion of components with (potential) hydrophilic groups in the total amount of all synthetic components is generally determined by the molar amount of (potential) hydrophilic groups from 30 to 1000, based on the mass of all monomers, It is preferably metered to 50 to 500 and particularly preferably 80 to 300 mmol / kg.

  The (latent) hydrophilic group may be a non-ionic hydrophilic group or advantageously a (latent) ionic hydrophilic group. As nonionic hydrophilic groups, in particular polyethylene glycol ethers from preferably 5 to 100, advantageously 10 to 80 ethylene oxide repeating units are taken into account. The content of polyethylene oxide units is generally 0-10% by weight, preferably 0-6% by weight, based on the weight of all monomers. Preferred monomers having nonionic hydrophilic groups are reaction products from polyethylene oxide diols having at least 20% by weight of ethylene oxide, polyethylene oxide monools and polyethylene glycols and diisocyanates having terminally etherified polyethylene glycol groups. is there. Such diisocyanates and their preparation are described in patent documents US-A 3,905,929 and US-A 3,920,598.

  Ionic hydrophilic groups are, among others, anionic groups such as sulfonate groups, carboxylate groups and phosphate groups in the form of alkali metal salts or ammonium salts and cationic groups such as ammonium groups, in particular protonated tertiary groups. An amino group or a quaternary ammonium group. Potential ionic hydrophilic groups are, among others, those that can be converted to the above ionic hydrophilic groups by a simple neutralization reaction, hydrolysis reaction or quaternization reaction, i.e. for example carboxylic acid groups or groups. Tertiary amino group. (Potential) ionic monomers are described in detail, for example, in Ullmanns Enzyklopaedie der technischen Chemie, 4th edition, volume 19, pages 311 to 313, and for example in DE-A 149574.

Among (potential) cationic monomers, monomers having a tertiary amino group are particularly important in practice, for example: tris- (hydroxyalkyl) -amine, N, N′-bis (hydroxy Alkyl) -alkylamines, N-hydroxyalkyl-dialkylamines, tris- (aminoalkyl) -amines, N, N′-bis (aminoalkyl) -alkylamines, N-aminoalkyl-dialkylamines, where The alkyl group and alkanediyl unit of the tertiary amine are composed of 1 to 6 C atoms independently of each other. Furthermore, preferably, as obtained per se in the usual way, for example by alkoxylation of amines having two hydrogen atoms bonded to the amine nitrogen, for example methylamine, aniline or N, N′-dimethylhydrazine, preferably Polyethers with tertiary nitrogen atoms with two terminal hydroxyl groups are taken into account. Such polyethers have a molecular weight generally between 500 and 6000 g / mol. These tertiary amines are used with acids, preferably strong mineral acids such as phosphoric acid, sulfuric acid, hydrohalic acids or strong organic acids, or with suitable quaternizing agents such as halogenated C _1. -C ₆ - alkyl or benzyl halide, for example by reaction with a bromide or chloride, be converted into an ammonium salt.

［式中、Ｒ¹及びＲ²はＣ₁〜Ｃ₄−アルカンジイル（単位）であり、かつ、Ｒ³はＣ₁〜Ｃ₄−アルキル（単位）である］の化合物及び、なかでもジメチロールプロピオン酸（ＤＭＰＡ）が有利である。さらに、相応するジヒドロキシスルホン酸及びジヒドロキシホスホン酸、例えば２，３−ジヒドロキシプロパンホスホン酸が適している。 As a monomer having a (potential) anionic group, usually an aliphatic, cycloaliphatic or aromatic fat having at least one alcoholic hydroxyl group or at least one primary amino group or secondary amino group Group or aromatic carboxylic acids and sulfonic acids are taken into account. Preference is given to dihydroxyalkyl carboxylic acids, especially those having 3 to 10 C atoms, as described, for example, in US Pat. No. 3,412,054. In particular, the general formula (c1)

[Wherein R ¹ and R ² are C ₁ -C ₄ -alkanediyl (unit) and R ³ is C ₁ -C ₄ -alkyl (unit)], and in particular dimethylol Propionic acid (DMPA) is preferred. Furthermore, the corresponding dihydroxysulfonic acids and dihydroxyphosphonic acids, for example 2,3-dihydroxypropanephosphonic acid, are suitable.

  In addition, the dihydroxyl compounds known from DE-A 3911827 having at least two carboxylate groups and having a molecular weight of more than 500 and up to 10000 g / mol are suitable. They are in a molar ratio of 2: 1 to 1.05: 1 in the polyaddition reaction between a dihydroxyl compound and a tetracarboxylic dianhydride, such as pyromellitic dianhydride or cyclopentane tetracarboxylic dianhydride. It is obtained by the reaction of Suitable dihydroxyl compounds are in particular monomers (b2) and diols (b1) mentioned as chain extenders.

  At least one of the polyurethanes, preferably not only the first polyurethane but also the second polyurethane has a carboxyl group. The carboxyl group has at least one alcoholic hydroxyl group or at least one primary or secondary amino group, the aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acids mentioned above Can be introduced into the polyurethane. Preference is given to dihydroxyalkyl carboxylic acids, in particular those having 3 to 10 C atoms, in particular dimethylolpropionic acid.

As further monomers having amino groups reactive towards isocyanates, aminocarboxylic acids, such as lysine, β-alanine or the α, β-unsaturated aliphatic diprimary diamines mentioned in DE-A 2034479. Adducts to saturated carboxylic or sulfonic acids are taken into account. Such compounds include, for example, formula (c2)
H2N-R4-NH-R5-X (c2)
[Wherein R ⁴ and R ⁵ , independently of one another, are C ₁ -C ₆ -alkanediyl units, preferably ethylene, and X is COOH or SO ₃ H]. Particularly advantageous compounds of the formula (c2) are N- (2-aminoethyl) -2-aminoethanecarboxylic acid and N- (2-aminoethyl) -2-aminoethanesulfonic acid or the corresponding alkali metal salts Here, Na is particularly advantageous as a counter ion. Further particularly advantageous are adducts of the above aliphatic diprimary diamines to 2-acrylamido-2-methylpropanesulfonic acid, as described, for example, in DE-B 1954090.

  If a monomer having a latent ionic group is used, the conversion of the monomer to the ionic form may take place before, during, but preferably after the isocyanate polyaddition, since This is because ionic monomers are often poorly soluble in the reaction mixture. The neutralizing agent is, for example, ammonia, NaOH, triethanolamine (TEA), triisopropylamine (TIPA), morpholine, or a derivative thereof. Particularly preferably, the sulfonate or carboxylate groups are present in the form of their salts with alkali metal ions or ammonium ions as counterions.

  The polyvalent monomer, which is also optionally a component of the polyurethane, is generally used for crosslinking or chain extension. They are generally one in addition to more than divalent non-phenolic alcohols, amines having two or more primary amino groups and / or secondary amino groups and one or more alcoholic hydroxyl groups. It is a compound having the above primary amino group and / or secondary amino group. Alcohols with a valency greater than 2 that can help control a certain degree of branching or crosslinking are, for example, trimethylolpropane, glycerin or sugars. Moreover, in addition to hydroxyl groups, monoalcohols having further groups reactive towards isocyanates, such as monoalcohols having one or more primary amino groups and / or secondary amino groups, such as mono Ethanolamine is taken into account. Polyamines having two or more primary amino groups and / or secondary amino groups are used, inter alia, when chain extension or crosslinking is to be carried out in the presence of water, since amines This is because it usually reacts with isocyanate more rapidly than alcohol or water. This is frequently required when an aqueous dispersion of crosslinked polyurethane or polyurethane with high molecular weight is desired. In such cases, prepolymers having isocyanate groups are produced, which are rapidly dispersed in water and subsequently chain extended or cross-linked by addition of compounds having multiple amino groups reactive with isocyanate. This is done. Suitable amines for this purpose are generally 32 to 500 g / mol, preferably 60 to 300 g, containing at least two amino groups selected from the group of primary amino groups and secondary amino groups. Polyfunctional amine in the molecular weight range of / mol. Examples in this regard are diamines such as diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethyl-cyclohexane (isophoronediamine, IPDA ), 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate or triamine, such as diethylenetriamine or 1,8-diamino-4-aminomethyloctane. The amines are in blocked form, for example the corresponding ketimines (see for example CA-A 1129128), ketazines (for example compare US-A 4,269,748) or amine salts (US-A 4,292, 226)). Oxazolidines, such as those used in US-A 4,192,937, for example, also represent capped polyamines that can be used for the production of polyurethanes according to the invention for chain extension of prepolymers. When such capped polyamines are used, they are generally mixed with the prepolymer in the absence of water, and the mixture is subsequently mixed with the dispersion or a portion of the dispersion. Thus, the corresponding polyamine is liberated by hydrolysis. Preference is given to using a mixture of diamine and triamine, particularly preferably a mixture of isophoronediamine (IPDA) and diethylenetriamine (DETA). The polyurethane preferably contains from 1 to 30 mol%, particularly preferably from 4 to 25 mol%, of polyamines having at least two amino groups reactive towards isocyanate, based on the total amount of all synthesis components. . Higher divalent isocyanates can also be used for the same purpose. Commercially available compounds are, for example, isocyanurates or hexamethylene diisocyanate biurets.

  Monovalent monomers optionally used in combination are monoisocyanates, monoalcohols and monoprimary amines and monosecondary amines. In general, their proportion is up to 10 mol%, based on the total molar amount of monomers. These monofunctional compounds usually have additional functional groups, such as olefin groups or carbonyl groups, and functional groups on the polyurethane that allow dispersion or crosslinking of the polyurethane or further polymerization-like reactions. Used to introduce. For this purpose, monomers such as isopropenyl-α, α-dimethylbenzyl isocyanate (TMI) and esters of acrylic acid or methacrylic acid such as hydroxyethyl acrylate or hydroxyethyl methacrylate are taken into account.

In the field of polyurethane chemistry, it is generally known how the molecular weight of polyurethane can be adjusted by the selection of the proportion of monomers reactive with each other as well as the arithmetic average of the number of reactive functional groups per molecule. Usually, the components as well as the respective molar amounts of the components are
The ratio A: B of the molar amount of A isocyanate group to the molar amount of B hydroxyl group and the molar amount of functional group capable of reacting with isocyanate in the addition reaction is 0.5: 1 to 2: 1, preferably 0 Very advantageously, the ratio A: B is chosen to be as close to 1: 1 as possible, chosen to be from 8: 1 to 1.5, particularly preferably from 0.9: 1 to 1.2: 1. On average, the monomers used are usually reacted in an addition reaction with 1.5 to 2.5, preferably 1.9 to 2.1, particularly preferably 2.0 isocyanate groups or isocyanates. It has a functional group that can.

  The polyaddition of synthetic components to produce polyurethanes is preferably carried out at normal or autogenous pressure at reaction temperatures of up to 180 ° C., advantageously up to 150 ° C. The production of polyurethanes or polyurethane aqueous dispersions is known to those skilled in the art.

  Ethylene / vinyl acetate in the sense of the present invention is a copolymer which is predominantly, ie, more than 50% by weight, preferably at least more than 60% by weight, or rather 100% by weight, synthesized from ethylene- and vinyl acetate monomers. It is. The ethylene / vinyl acetate mass ratio is then preferably 1 or less, in particular less than 0.66 or less than 0.4. The further monomer may be, for example, an acrylic ester or methacrylic ester in an amount of 0 to less than 50% by weight, in particular less than 1 to 35% by weight.

  The polyurethane and ethylene / vinyl acetate copolymer are preferably present as an aqueous dispersion and are used in this form.

［式中、Ｒ¹〜Ｒ⁴は、互いに無関係に、有機基又はヒドロキシ基であり、ただし、基Ｒ¹〜Ｒ⁴の少なくとも２個は、ヒドロキシ基及びアルコキシ基から選択される基であり、かつ、残りの基Ｒ¹〜Ｒ⁴の少なくとも１個は、第１級アミノ基、第２級アミノ基、酸基、酸無水物基、カルバメート基、イソシアネート基、ヒドロキシル基及びエポキシ基から選択される少なくとも１個の官能基を含有する有機基である］を有する。 The silane compound used in the adhesive according to the invention is preferably of the formula

[Wherein, R ^{1 to} R ⁴ independently represent an organic group or a hydroxy group, provided that at least two of the groups R ^{1 to} R ⁴ are groups selected from a hydroxy group and an alkoxy group; And at least one of the remaining groups R ^{1 to} R ⁴ is selected from a primary amino group, a secondary amino group, an acid group, an acid anhydride group, a carbamate group, an isocyanate group, a hydroxyl group and an epoxy group. It is an organic group containing at least one functional group.

Preferably two or three, particularly preferably three, of the radicals R ^{1 to} R ⁴ are hydroxy or alkoxy groups. In general, they are alkoxy groups, and for later use, the alkoxy groups hydrolyze to form hydroxy groups, which then react further or crosslink. Particularly important are C ₁ -C ₉ alkoxy groups, preferably C ₁ -C ₆ alkoxy groups, particularly preferably C ₁ -C ₃ alkoxy groups, very particularly preferably methoxy or ethoxy groups, The methoxy group is important.

The remaining groups R ^{1 to} R ⁴ are organic groups whose molecular weight is generally less than 500 g / mol, in particular less than 200 g / mol, particularly preferably less than 150 g / mol or less than 100 g / mol. The remaining groups R ^{1 to} R ⁴ are, for example, an aliphatic or aromatic hydrocarbon group or a hydrocarbon group having not only an aliphatic component and an alicyclic component but also an aromatic component. Good. At least one of the remaining groups R ^{1 to} R ⁴ is at least selected from a primary amino group or a secondary amino group, an acid group, an acid anhydride group, a carbamate group, a hydroxyl group, an isocyanate group or an epoxy group. An organic group containing one functional group. Particularly preferred as functional groups are primary or secondary amino groups, epoxy groups, in particular glycidyl groups, or carbamate groups. Particular preference is given to epoxy groups, in particular glycidyl groups. The remaining groups R ^{1 to} R ⁴ may contain a plurality of functional groups, for example, two primary amino groups, two secondary amino groups, or a primary amino group and a secondary amino group. Good.

In the case of advantageous silanes, three of the groups R ^{1 to} R ⁴ are hydroxy groups or alkoxy groups (preferably alkoxy groups, see above) and the remaining one group is at least one It is an organic group having a functional group of Equally advantageous is that two of the radicals R ^{1 to} R ⁴ are hydroxy groups or alkoxy groups (preferably alkoxy groups, see above), and the remaining two groups are each at least 1 It is a silane that is an organic group having individual functional groups. Particular preference is given to glycidoxyalkyltrialkoxysilanes each having 1 to 5 C atoms in the alkyl group and in the alkoxy group. Considered as silanes are, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, 3- (Triethoxysilyl) propyl succinic anhydride, N-trimethoxysylmethyl-O-methylcarbamate.

  Suitable silanes are especially low-molecular and have a molecular weight of less than 5000 g / mol, in particular less than 2000 g / mol, particularly preferably less than 1000 g / mol and very particularly preferably less than 500 g / mol. The molecular weight is generally higher than 50 g / mol, in particular higher than 100 g / mol or 150 g / mol.

  The silane compound is preferably present in an amount greater than 0.2 parts by weight, in particular greater than 1 part by weight or greater than 2 parts by weight per 100 parts by weight of polyurethane and per 100 parts by weight of polyurethane. It is preferably used in an amount of up to 30 parts by weight, in particular in an amount of up to 20 parts by weight, particularly preferably in an amount of up to 10 parts by weight.

  The main component of the first adhesive component is a mixture of first and second polymers as a binder. The first adhesive component is preferably at least 20% by weight, particularly advantageously at least 30%, based on solids, ie water-free or otherwise liquid at 21 ° C. and 1 bar. % By weight, very preferably at least 40% by weight, and in particular at least 50% by weight, or at least 70% by weight, consists of a mixture of the first and second polymers. The first adhesive component is aqueous, i.e. it contains water as the main or sole solvent or dispersant.

  The first adhesive component may consist only of a mixture of the first and second polymers, apart from the water or other solvent that escapes upon drying. It contains further additives such as further binders, stabilizers, fillers, thickeners, wetting aids, antifoaming agents, crosslinking agents, anti-aging agents, fungicides, pigments, soluble dyes, Matting agents and neutralizing agents may also be included. Further additives may be added in a simple manner to the mixture of the first and second polymers or to the aqueous dispersion of the mixture. As stabilizers, basically those that are normally used in the case of aqueous dispersions are suitable. It is a stabilizer selected from the group comprising wetting agents, cellulose, polyvinyl alcohol, polyvinylpyrrolidone and mixtures thereof that results in a storage stable polymer dispersion composition. The subject of the invention therefore also contains at least one further additive in an adhesive as described above, which additive further comprises further binders, stabilizers, fillers. An adhesive characterized in that it is selected from thickeners, wetting aids, antifoaming agents, crosslinking agents, anti-aging agents, fungicides, pigments, soluble dyes, matting agents and neutralizing agents.

As further binders which can be used in the mixture with the first and second polymers, in particular radically polymerized polymers are considered, preferably in the form of their aqueous dispersions. Such polymers are preferably at least 60% by weight, C ₁ -C ₂₀ alkyl (meth) acrylates, vinyl esters of carboxylic acids containing up to 20 C atoms, vinylaromatics having up to 20 C atoms , Ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 C atoms, aliphatic hydrocarbons having 2 to 8 C atoms and one or two double bonds, or monomers thereof It consists of so-called main monomers selected from mixtures. The particular thing to be mentioned polymers, more than 60% by weight, C ₁ -C ₂₀ alkyl (meth) (polyacrylates for short) polymer which is composed of acrylate, or more than 60% by weight of styrene And 1,3-butadiene polymers (styrene / butadiene copolymers, especially carboxylated styrene / butadiene copolymers). The carboxylated styrene / butadiene copolymer comprises styrene, butadiene and at least one ethylenically unsaturated group having at least one carboxyl group such as acrylic acid, methacrylic acid, fumaric acid, itaconic acid, preferably acrylic acid. It is formed from the radically polymerizable monomer.

  In a special embodiment, the adhesive does not contain yet another type of binder in addition to the first and second polymers. In other embodiments, the adhesive comprises 10 additional binders, preferably polyacrylates and / or styrene / butadiene copolymers, different from the first and second polymers, based on the total amount of all adhesive polymers. -50 mass parts or 20-50 mass parts or 30-50 mass parts is contained.

  Yet another component of the adhesive may be, for example, yet another crosslinker. Considered are, for example, compounds with chemically blocked isocyanates, encapsulated isocyanates, encapsulated uretdiones, biurets or allophanate or carbodiimide groups. The additional cross-linking agent may be bound to the polyurethane, but may be a compound that is dissolved or dispersed in the polyurethane. The adhesive does not require additional cross-linking agents to achieve the desired properties, and therefore preferably the adhesive does not contain any additional cross-linking agents.

  Particularly preferred are compositions which are free of organic solvents, in particular free of so-called VOCs (Volatile Organic Compounds) and / or free of plasticizers. Both plasticizers and organic solvents are harmful from an environmental toxicological and occupational health standpoint. The plasticizer can flow on the surface and damage the bond or make the surface sticky, resulting in soiling of the bond line. Solvents are also not desired, since they can, on the one hand, have additional risk potential on heating and on application of the adhesive, and on the other hand the solvents are similar. And may be released to the environment and the material in contact with the adhesive over a long period of time and may adversely affect them or damage the bond. Therefore, the first adhesive component is preferably a purely aqueous system with water as the only solvent or as the only dispersion medium. The solid content, that is, the content of all components other than water or substances that are liquid at 21 ° C. and 1 bar other than water, is preferably 20 to 80% by mass.

  The subject of the invention also contains at least one first polymer and at least one second polymer different from the first polymer for producing the adhesive according to the invention described above. Wherein the first polymer is selected from a polymer capable of forming a crystalline domain and a copolymer of ethylene and vinyl acetate, and the second polymer is an amorphous polyurethane, and Wherein at least one of both polymers has a carboxyl group, wherein the mass ratio of the first polymer to the second polymer is from 2: 8 to 8: 2. The subject of the present invention is also the use of the adhesive according to the invention as described above for the production of film-laminated molded parts for automobile production, which have a high climate change stability.

  The adhesive according to the invention can be used as a two-component (2K) adhesive. In the case of 2K adhesives, yet another additive, generally a cross-linking agent, in this case silane, is added before use. Particularly suitable for producing composites, in particular by permanently bonding a large area flexible first substrate to a festen Formkoerper as a second substrate. The adhesive according to the present invention as a laminating adhesive. The first substrate of large area is selected in particular from polymer films, paper, metal films, veneers and fiber nonwovens from natural or synthetic fibers. They are glued together or preferably glued to a solid shaped body, for example a molded part made of metal, painted metal, wood, wood material, fiber material or plastic.

The subject of the invention is also a process for the production of film-laminated molded parts, in particular for the manufacture of automobiles, where a) a first adhesive component according to the invention as described above and a second according to the invention as described above. The adhesive component, the polymer film and the molded member, for example, intended for attachment to an automobile,
b) Mixing the adhesive components and applying to the polymer film and / or molded part, and c) subsequently bonding the polymer film to the molded part under pressure and / or elevated temperature.

  The composite produced according to the present invention has an additional primer layer for improved adhesion between the first substrate and the adhesive layer and / or between the second substrate and the adhesive layer. You can do it. The substrate or molded member to be bonded may be pretreated with an adhesion promoter. However, based on the already good adhesive properties of the adhesive according to the invention, the use of a primer is not always necessary.

  Particularly advantageous as the first substrate is a polymer film. A polymer film is in particular understood as a flexible planar plastic that is 0.05 mm to 5 mm thick and can be wound up. Therefore, in addition to “film” in the strict sense of a thickness of 1 mm or less, it is generally 1 to 3 mm thick for sealing tunnels, roofs or swimming pools, in special cases, on the contrary It is also understood as a sealing sheet used in a thickness of up to 5 mm. Such plastic films are usually produced by spread molding, casting, calendering or extrusion and are generally commercially available in roll form or manufactured in situ. They may consist of a single layer or multiple layers. The plastics of the polymer film are preferably thermoplastics, for example polyesters such as polyethylene terephthalate (PET), thermoplastic polyolefins (TPO) such as polyethylene, polypropylene, polyvinyl chloride, in particular soft PVC, polyacetate, ethylene / acetic acid. Vinyl copolymers (EVA), ASA (acrylonitrile / styrene acrylate copolymer), PUR (polyurethane), PA (polyamide), poly (meth) acrylate, polycarbonate, or plastic alloys thereof, in particular foamed PVC It is also a film and a foamed thermoplastic polyolefin film (TPO). Particularly advantageous are PVC and thermoplastic polyolefin films (TPO).

  The molded part may be a molded part composed of synthetic fibers or natural fibers or chips, which are joined by a binder to form a molded part; in particular, a molded part from plastic, for example ABS Is also suitable. The molded member may have any shape.

  Coating of the base material and the molded member with the adhesive may be performed by, for example, spray coating, brush coating, blade coating, die coating, roll coating, or casting coating according to a normal coating method. Preference is given to spray application.

Amount of adhesive to be applied, based on the adhesive, preferably 0.5 to 100 g / m ^2, particularly preferably 2~80g / m ^2, is very advantageous and 10~70g / m ^2. Preferably, only the substrate to be bonded is coated on one side, for example only the film or only the molded part. However, the two units to be bonded are also considered, namely the film and the coating of the molded part. After coating, drying is usually performed preferably at room temperature or temperatures up to 80 ° C. to remove water or other solvents.

Substrates or molded parts coated with one or two adhesive components can be stored prior to bonding. A flexible base material can be wound up with a roll, for example. For bonding, the members to be bonded are combined. The adhesive is activated by heat. The temperature in the adhesive layer is preferably at least 30 ° C or at least 50 ° C, for example 30-200 ° C, or 50-180 ° C or 60-80 ° C. Adhesion is preferably performed under pressure. For this purpose, for example, the member to be bonded is at least 0.005 or at least 0.01 or at least 0.08 N / mm ² , for example 0.005 to 5 N / mm ² or 0.01 to 0.8 N / mm. ^They may be pressed against each other with a pressure of ² . The pressing force may be created, for example, by applying a negative pressure between the film and the substrate and / or by air pressure.

  The resulting composites are distinguished by having high mechanical strength even at elevated temperatures (thermal stability) or under severely changing climatic conditions (climate stability).

  The method according to the invention is particularly advantageous for producing mounting parts for vehicles, and is particularly advantageous in that the adhesive according to the invention is used for producing automotive interior parts. Examples of such interior components are door lining, switchboard, instrument panel, rear panel (Hutablagen), roof panel lining (Fertighimmel), sliding roof panel lining (Shiebehimmel), center console, glove box, sun visor, pillar, door handle And armrests, floor assemblies, load floor assemblies and trunk assemblies and light van and truck nap corner walls and rear walls. For this, in particular vacuum deep drawing or press lamination is used in the sealing process. In the case of the vacuum deep drawing method, an adhesive is applied to the molded body. Subsequently, aeration is optionally carried out in the drying duct, for example at room temperature or preferably at a maximum of 40 ° C. In general, a film to be glued, for example a decorative film from an air-impermeable material, is hermetically fixed in the frame. A lower mold exists below the film, and the lower mold and the molded body on which the molded body is placed have a through-hole or are air permeable. The device is further hermetically sealed down. When the air is evacuated from the device, the film then matches the compact exactly under pressure on its surface. The film is heated before applying a vacuum or negative pressure. The film is air impermeable because of the vacuum created or negative pressure. In the case of the press lamination method, the adhesive is likewise applied to the shaped body and optionally to the film to be bonded, but at least to the shaped body. Subsequently, aeration is optionally carried out in the drying duct, generally at room temperature or preferably at a maximum of 40 ° C. Adhesion between the molded body and the film is performed while bonding and pressure bonding after thermal activation. The film used here is frequently a plastic decorative film and may have a surface structure. This surface structure on the plastic film may for example be typed before, during or after bonding.

All percentage values in the examples are mass values unless otherwise stated. The content value relates to the content in an aqueous solution or dispersion. The measurement of the viscosity may be carried out using a rotational viscometer at a temperature of 23 ° C. according to DIN EN ISO 3219.

Substances used:
Silane: Geniosil ^(R) GF 80 is available as 3-glycidoxypropyltrimethoxysilane (Wacker-Chemie GmbH)
Crystalline polyurethane:
^{Luphen (R) D 207 E;} BASF SE are marketed for industrial lamination than a polyester having units derived from a polyester diol - Polyurethane - aqueous dispersion of the elastomer. After film formation of the dispersion, a polymer film containing crystal domains results. 45 mass% solids; pH 6.5-8.5; viscosity 50-180 mPas (23 ° C., 250 s ⁻¹ ).

Amorphous polyurethane, PU-1:
A polyurethane dispersion prepared from poly (tetrahydrofuran) having a molecular weight Mn of about 2000, dimethylolpropionic acid, isophorone diisocyanate and isophoronediamine and neutralized with triethylamine. After film formation of the dispersion, a polymer film containing no crystalline domains is produced. Solid content 50% by mass; K value 40, viscosity 68 mPas, pH 6.8 (23 ° C.).

Amorphous polyurethane, PU-2:
A polyurethane dispersion prepared from poly (propylene oxide) having a molecular weight Mn of about 2000, dimethylolpropionic acid, neopentyl glycol, tolylene diisocyanate and neutralized with NaOH. After film formation of the dispersion, a polymer film containing no crystalline domains is produced. Solid content 40% by mass; K value 47, viscosity 167 mPas, pH 7.6.

Ethylene / vinyl acetate copolymer:
Airflex ^(R) EP 17; ethylene / 60 wt% of a dispersion of vinyl acetate copolymer;
Viscosity 3800 ⁺ / _- 1000mPas (Brookfield RVT, Spindle 3,20rpm);
pH 4-5 (23 ° C).

Adhesive manufacturing:
The dispersion components (see Table 1) were charged to a stirred vessel and the silane was subsequently introduced with stirring. The adhesive represented by V is a comparative composition not according to the present invention.

Stability test in climate change test Adhesive (wet) 100-110 g / m ² is molded into a molded part (Rocoll GmbH, grain finish) consisting of ABS (Sabic, Cycolac G360 standard black) used in the manufacture of automotive interior parts: Ford Floor Grain 89/030, 40 μm) was applied by compressed air injection (Krautzberger GmbH, HS-25 HVLP) and dried at room temperature for 90 minutes. The molded member has a V-shaped cross section. The outer edge has a length of 200 mm and a width of 145 mm. The angle in the middle of the outer edge is 105 ° C. A film from soft PVC (Benecke Kaliko, Yorn ^(R) , Material No. V3569838Z1750A, color: black, thickness: 1.2 mm, length: 160 mm) was laminated to an ABS substrate. Lamination by thermal activation was performed using a thermoforming-uppress press (Buerkle, model Lamp 0909/60) in a vacuum deep drawing lamination method. After a preheating time of 80 seconds and application of a vacuum for 60 seconds, lamination was carried out at a pressing temperature of 121 ° C. for 45 seconds at 4.5 bar.

The laminated molded parts were subjected to the following test cycles in a climate test cabinet (Weiss Umwelttechnik GmbH, SB / 22/300/40):
1) Storage at 90 ° C. for 4 hours (relative humidity 80%)
2) Cooling to -30 ° C for 2 hours 3) Storage at -30 ° C for 4 hours (relative humidity 10%)
4) Heating to 90 ° C. for 2 hours After the complete test cycle has passed, the composite is examined for release of the flexible PVC film from the substrate. The test cycle is repeated until the first peel is clearly visible. For evaluation, record the maximum number of test cycles that the composite without delamination can withstand. The results are summarized in Table 2.

  Table 2 clearly shows the advantages of the adhesive according to the invention, since the composite has a clearly better behavior than the comparative composition with regard to climate change stability.

Claims (17)

An adhesive from a first aqueous component and from a second component, wherein the first component comprises at least one first polymer and at least one different from the first polymer Containing a second polymer of the species,
Wherein the first polymer is selected from polymers capable of forming crystalline domains, copolymers from ethylene and vinyl acetate, and mixtures thereof;
And the second polymer is an amorphous polyurethane,
And wherein at least one of both polymers has a carboxyl group,
Wherein the mass ratio of the first polymer to the second polymer is from 2: 8 to 8: 2, and
Here, the second component contains at least one silane compound reactive to a carboxyl group, and includes an adhesive from the first aqueous component and the second component.   The adhesive of claim 1, wherein the first polymer has a heat of fusion of at least 20 J / g when present as a polymer film.   The first polymer is selected from the group consisting of polyurethanes forming crystalline domains and ethylene / vinyl acetate copolymers having units derived from polyester diol, and the second polymer is a polyether diol 3. Adhesive according to claim 1 or 2, characterized in that it is an amorphous polyurethane having units derived from. The first polymer is a polyurethane and has units derived from a polyester diol, and the second polymer is a polyurethane and has units derived from a polyether diol;
And where at least one of both polyurethanes has a carboxyl group,
Wherein the mass ratio of the sum of all units derived from the polyester diol to the sum of all units derived from the polyether diol is from 2: 9 to 7: 2. The adhesive according to any one of 3 to 3. The first component is
(A) (i) polyurethanes having crystalline domains and having units derived from polyester diols and no units derived from polyether diols and (ii) ethylene / vinyl acetate copolymers or their 20-80 parts by weight of at least one first polymer selected from the mixture,
(B) 20-80 parts by weight of at least one amorphous polyurethane having units derived from polyether diol and not having units derived from polyester diol; and (c) (a) and The adhesive according to any one of claims 1 to 4, further comprising 0 to 50 parts by mass of another polymer different from (b). The first polymer is
a) diisocyanate,
b) a polyester diol having a molecular weight of greater than 500 to 5000 g / mol,
c) a diol having a carboxylic acid group, and d) optionally a reactive group selected from an alcoholic hydroxy group, a primary amino group, a secondary amino group and an isocyanate group different from a) to c). A polyurethane synthesized from still another monovalent compound or polyvalent compound,
And the second polymer is
a) diisocyanate,
b) a polyether diol having a molecular weight of 240 to 5000 g / mol,
c) a diol having a carboxylic acid group, and d) optionally a reactive group selected from an alcoholic hydroxy group, a primary amino group, a secondary amino group and an isocyanate group different from a) to c). The adhesive according to any one of claims 1 to 5, wherein the adhesive is synthesized from another monovalent compound or polyvalent compound.   The second polymer is a polyurethane having units derived from a polyether diol, and the polyether diol is selected from polytetrahydrofuran and polypropylene oxide; and the first polymer is a polyurethane. And having a unit derived from a polyester diel, and the polyester diol is selected from a reaction product of a dihydric alcohol and a divalent carboxylic acid and a lactone-based polyester diol The adhesive according to any one of claims 1 to 6. formula

[Wherein, R ^{1 to} R ⁴ independently represent an organic group or a hydroxy group, provided that at least two of the groups R ^{1 to} R ⁴ are groups selected from a hydroxy group and an alkoxy group; And at least one of the remaining groups R ^{1 to} R ⁴ is selected from a primary amino group, a secondary amino group, an acid group, an acid anhydride group, a carbamate group, an isocyanate group, a hydroxyl group and an epoxy group. It is an organic group containing at least one functional group]. The adhesive according to any one of claims 1 to 7, The adhesive according to claim 8, wherein two or three of the groups R ^{1 to} R ⁴ are alkoxy groups.   10. The silane compound according to claim 1, wherein the silane compound is a glycidoxyalkyltrialkoxysilane having 1 to 5 C atoms in the alkyl group and in the alkoxy group, respectively. Glue.   The adhesive according to any one of claims 1 to 10, wherein the silane is used in an amount of more than 0.2 parts by mass and up to 30 parts by mass per 100 parts by mass of the polymer.   Containing at least one further additive, wherein the additive is further a binder, stabilizer, filler, thickener, wetting aid, antifoaming agent, cross-linking agent, anti-aging agent, 12. Adhesive according to any one of claims 1 to 11, characterized in that it is selected from fungicides, pigments, soluble dyes, matting agents and neutralizing agents.   13. Adhesive according to any one of claims 1 to 12, characterized in that the polyurethane is dispersed in water and is therefore an aqueous polyurethane dispersion.   14. Adhesive according to any one of the preceding claims, characterized in that the first polymer is a crystalline polyurethane in the pure state and has a melting point in the range of 30-150 [deg.] C. .   15. Use of an adhesive according to any one of claims 1 to 14 for the production of film-laminated molded parts for automobile production having high climate change stability. A method for producing a molded member laminated with a film for automobile production,
A) using a first adhesive component and a second adhesive component according to any one of claims 1 to 14, a polymer film, and a molding member scheduled for attachment to an automobile. ,
b) mixing the adhesive component and applying it to the polymer film and / or molded part; and c) subsequently bonding the polymer film to the molded part under pressure and / or elevated temperature.
A method for producing a film-laminated molded member for automobile production.   A composite from a solid molded body, wherein a flexible film is adhered by the adhesive according to any one of claims 1 to 14.